RESUMEN
To clarify the key role of oxygen vacancy defects on enhancing the oxidative activity of the catalysts, metal-organic frameworks (MOFs) derived MnOX catalysts with different morphologies and oxygen vacancy defects were successfully prepared using a facile in-situ self-assembly strategy with different alkali moderators. The obtained morphologies included three-dimensional (3D) triangular cone stacked MnOX hollow sphere (MnOX-H) and 3D nanoparticle stacked MnOX nanosphere (MnOX-N). Compared to MnOX-N, MnOX-H exhibited higher activity for the oxidation of toluene (T90 = 226 °C). This was mainly due to the large number of oxygen vacancy defects and Mn4+ species in the MnOX-H catalyst. In addition, the hollow structure of MnOX-H not only facilitated toluene adsorption and activation of toluene and also provided more active sites for toluene oxidation. Reaction mechanism studies showed that the conversion of toluene to benzoate could be realized over MnOX-H catalyst during toluene adsorption at room temperature. In addition, abundant oxygen vacancy defects can accelerate the activated oxidation of toluene and the formation of oxidation products during toluene oxidation.
RESUMEN
In this research, a range of Pt/CeO2 catalysts featuring varying Pt-O-Ce bond contents were developed by modulating the oxygen vacancies of the CeO2 support for toluene abatement. The Pt/CeO2-HA catalyst generated a maximum quantity of Pt-O-Ce bonds (possessed the strongest metal-support interaction), as evidenced by the visible Raman results, which demonstrated outstanding toluene catalytic performance. Additionally, the UV Raman results revealed that the strong metal-support interaction stimulated a substantial increase in oxygen vacancies, which could facilitate the activation of gaseous oxygen to generate abundant reactive oxygen species accumulated on the Pt/CeO2-HA catalyst surface, a conclusion supported by the H2-TPR, XPS, and toluene-TPSR results. Furthermore, the results from quasi-in situ XPS, in situ DRIFTS, and DFT indicated that the Pt/CeO2-HA catalyst with a strong metal-support interaction led to improved mobility of reactive oxygen species and lower oxygen activation energies, which could transfer a large number of activated reactive oxygen species to the reaction interface to participate in the toluene oxidation, resulting in the relatively superior catalytic performance. The approach of tuning the metal-support interaction of catalysts offers a promising avenue to develop highly active catalysts for toluene degradation.
RESUMEN
Tubular, pie- and bread-shaped forms of Co3O4 with exposed {110}, {112} and {111} facets were prepared and compared in their photothermal catalytic performance and reaction pathways during the oxidation of methanol. Among them, the Co3O4 with exposed {110} facet exhibited the best photothermal catalytic performance (95% methanol conversion, 93% CO2 yield) under solar irradiation, while also maintaining good stability and moisture resistance. Reaction mechanism studies showed that the {110} facets had a strong adsorption capacity for formaldehyde, which facilitated its conversion to formate. The transformation of formaldehyde to formate species was the key step. The key step on the {110} facet was conversion of formaldehyde to a mono-dentate formate species, while conversion on the {112} and {111} facets was mainly to bi-dentate formate species. This study demonstrated that the design of preferential exposed crystal facet can regulate the pathway of photothermal catalytic reaction and realize efficient solar energy utilization.
RESUMEN
Series of Co3+-rich spinel Co3O4 catalysts were synthesized and evaluated by toluene catalytic oxidation. An outstanding activity was achieved over Co3O4-N utilizing Co(NO3)2·6H2O as precursor (T50 = 211 °C, T90 = 217 °C at conditions: 1000 ppm(v), WHSV = 60 000 mL g-1 h-1). Results of comparative characterizations demonstrated that such excellent performance was mainly attributed to large surface area, high reducibility at low temperature, high abundance of Co3+ ions and structure defects, as well as highly active surface oxygen. The results of in situ DRIFTS revealed that in the air or N2 atmosphere, the by-products were almost the same. The reaction pathway of toluene oxidation can be described as follow: transformation of toluene from benzyl alcohol, benzaldehyde, benzoate, benzene, phenol, benzoquinone, maleic acid and to final products, which were fully confirmed by PTR-TOF-MS. Besides, ring opened by-products, such as acetone, acetic acid, acetaldehyde, etc. were also detected. In this work, the combination of in situ DRIFTS and PTR-TOF-MS provided a promising approach for further understanding of the mechanism of VOCs elimination.